Reversible Electrochemical Gelation of Metal Chalcogenide Quantum Dots.

The ability to dictate the assembly of quantum dots (QDs) is critical for their integration into solid-state electronic and optoelectronic devices. However, assembly methods that enable efficient electronic communication between QDs, facilitate access to the reactive surface, and retain the native quantum confinement characteristics of the QD are lacking. Here we introduce a universal and facile electrochemical gelation method for assembling metal chalcogenide QDs (as demonstrated for CdS, ZnS, and CdSe) into macroscale 3-D connected pore-matter nanoarchitectures that remain quantum confined and in which each QD is accessible to the ambient. Because of the redox-active nature of the bonding between QD building blocks in the gel network, the electrogelation process is reversible. We further demonstrate the application of this electrogelation method for a one-step fabrication of CdS gel gas sensors, producing devices with exceptional performance for NO2 gas sensing at room temperature, thereby enabling the development of low-cost, sensitive, and reliable devices for air quality monitoring.

Effect of metal ion solubility on the oxidative assembly of metal sulfide quantum dots.

The versatility of the oxidative assembly method for the creation of 2D and 3D quantum dot (QD) architectures represents both an opportunity and a challenge as a method enabling controlled placement of chemically distinct QDs in multicomponent systems. The opportunity lies in the ability to independently tune the kinetics of the different components so that they are similar (leading to well-mixed systems) or different (enabling gradient or phase-segregated composites) using a wide range of variables; the challenge lies in understanding those variables and how their interplay affects the overall kinetics. Here, we show that the identity of the cation in the sulfide matrix (M = Cd2+ vs Zn2+) plays a large role in the kinetics of assembly of mass spectrometry QDs, attributed to differences in solubility. Time resolved dynamic light scattering is used to monitor the hydrodynamic radius, R¯h. ZnS shows an exponential growth associated with reaction-limited cluster aggregation (RLCA), whereas CdS demonstrates a significant induction period (10-75 min) followed by a growth step that cannot be distinguished between RLCA and diffusion limited cluster aggregation. These data correlate with relative solubilities of the nanoparticles, as probed by free-cation concentration. Data also confirm prior studies showing that cubic-closest-packed (ccp) lattices are kinetically slow relative to hexagonally closest-packed (hcp); using the slope of the ln R¯h vs time plot for the rate constant, the values of 0.510 s-1 and 3.92 s-1 are obtained for ccp ZnS and hcp ZnS, respectively. Thus, both the structure and the solubility are effective levers for adjusting the relative reactivity of QDs toward oxidative assembly.

Electrochemical gelation of quantum dots using non-noble metal electrodes at high oxidation potentials.

Relative to conventional chemical approaches, electrochemical assembly of metal chalcogenide nanoparticles enables the use of two additional levers for tuning the assembly process: electrode material and potential. In our prior work, oxidative and metal-mediated pathways for electrochemical assembly of metal chalcogenide quantum dots (QDs) into three-dimensional gel architectures were investigated independently by employing a noble-metal (Pt) electrode at relatively high potentials and a non-noble metal electrode at relatively low potentials, respectively. In the present work, we reveal competition between the two electrogelation pathways under the condition of high oxidation potentials and non-noble metal electrodes (including Ni, Co, Zn, and Ag), where both pathways are active. We found that the electrogel structure formed under this condition is electrode material-dependent. For Ni, the major phase is oxidative electrogel, not a potential-dependent mixture of oxidative and metal-mediated electrogel that one would expect. A mechanistic study reveals that the metal-mediated electrogelation is suppressed by dithiolates, a side product from the oxidative electrogelation, which block the Ni electrode surface and terminate metal ion release. In contrast, for Co, Ag, and Zn, the electrode surface blockage by dithiolates is less effective than for Ni, such that metal-mediated electrogelation is the primary gelation pathway.

Exploiting kinetics for assembly of multicomponent nanoparticle networks with programmable control of heterogeneity.

Kinetic control of metal chalcogenide nanoparticle oxidative assembly is realized by varying the redox potential of the chalcogenide, structure (wurtzite vs. zinc blende), and ligand chain length. This knowledge is exploited to form two-component (ZnS + CdSe) hybrid aerogels with minimal heterobonding (phase-segregated) or maximal heterobonding (intimately mixed).